cis-selective single-cleavage skeletal rearrangement of 1,6-enynes reveals the multifaceted character of the intermediates in metal-catalyzed cycloisomerizations

Angewandte Chemie - International Edition

Volumn 47, Issue 41, 2008, Pages 7892-7895

  Jiménez Núñez, Eloísa ^a,b   Claverie, Christelle K ^a   Bour, Christophe ^a   Cárdenas, Diego J ^b   Echavarren, Antonio M ^a,b  

^a INSTITUTE OF CHEMICAL RESEARCH OF CATALONIA ICIQ   (Spain)

^b UNIVERSIDAD AUTÓNOMA DE MADRID   (Spain)

Author keywords

Carbocations; Enynes; Gold; Metal carbenes; Rearrangement

Indexed keywords

EID: 54749146657     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.200803269     Document Type: Article

References (65)

1. a) V. Michelet, P. Y. Toullec, J. P. Genét, Angew. Chem. 2008, 120, 4338-4386;
2. Angew. Chem. Int. Ed. 2008, 47, 4268-4315;
3. b) A. S. K. Hashmi, Chem. Rev. 2007, 107, 3180-3211;
4. c) A. Fürstner, P. W. Davies, Angew. Chem. 2007, 119, 3478-3519;
5. Angew. Chem. Int. Ed. 2007, 46, 3410-3449;
6. d) D. J. Gorin, F. D. Toste, Nature 2007, 446, 395-403;
7. e) E. Jiménez-Núñez, A. M. Echavarren, Chem. Commun. 2006, 333-346;.
8. a) L. Zhang, J. Sun, S. A. Kozmin, Adv. Synth. Catal. 2006, 348, 2271-2296;
9. b) E. Jiménez-Núñez, A. M. Echavarren, Chem. Rev. 2008, 108, 3326-3350.
10. a) B. M. Trost, G. J. Tanoury, J. Am. Chem. Soc. 1988, 110, 1636-1638;
11. b) B. M. Trost, M. K. Trost, Tetrahedron Lett. 1991, 32, 3647-3650;
12. c) B. M. Trost, G. A. Doherty, J. Am. Chem. Soc. 2000, 122, 3801-3810;
13. d) B. M. Trost, M. Yanai, K. Hoogsteed, J. Am. Chem. Soc. 1993, 115, 5294-5295.
14. a) N. Chatani, T. Morimoto, T. Muto, S. Murai, J. Am. Chem. Soc. 1994, 116, 6049-6050;
15. b) N. Chatani, N. Furukawa, H. Sakurai, S. Murai, Organometallics 1996, 15, 901-903;
16. c) N. Chatani, H. Inoue, T. Morimoto, T. Muto, S. Murai, J. Org. Chem. 2001, 66, 4433-4436;
17. d) N. Chatani, H. Inoue, T. Kotsuma, S. Murai, J. Am. Chem. Soc. 2002, 124, 10294-10295;
18. e) Y. Miyanohana, Inoue, H. N. Chatani, J. Org. Chem. 2004, 69, 8541-8543;
19. f) Y. Miyanohana, N. Chatani, Org. Lett. 2006, 8, 2155-2158;
20. g) H. Nakai, N. Chatani, Chem. Lett. 2007, 1494-1495.
21. a) A. Fürstner, H. Szillat, F. Stelzer, J. Am. Chem. Soc. 2000, 122, 6785-6786;
22. b) A. Fürstner, F. Stelzer, H. Szillat, J. Am. Chem. Soc. 2001, 123, 11863-11869;
23. c) A. Fürstner, H. Szillat, B. Gabor, R. Mynott, J. Am. Chem. Soc. 1998, 120, 8305-8314.
24. S. Oi, I. Tsukamoto, S. Miyano, Y. Inoue, Organometallics 2001, 20, 3704-3709.
25. C. H. Oh, S. Y. Bang, C. Y. Rhim, Bull. Korean Chem. Soc. 2003, 24, 887-888.
26. G. B. Bajracharya, I. Nakamura, Y. Yamamoto, J. Org. Chem. 2005, 70, 892-897.
27. a) M. Méndez, M. P. Muñoz, A. M. Echavarren, J. Am. Chem. Soc. 2000, 122, 11549-11550;
28. b) M. Méndez, M. P. Muñoz, C. Nevado, D. J. Cárdenas, A. M. Echavarren, J. Am. Chem. Soc. 2001, 123, 10511-10520.
29. S. M. Kim, S. I. Lee, Y. K. Chung, Org. Lett. 2006, 8, 5425-5427.
30. a) C. Nieto-Oberhuber, M. P. Muñoz, E. Buñuel, C. Nevado, D. J. Cárdenas, A. M. Echavarren, Angew. Chem. 2004, 116, 2456-2460;
31. Angew. Chem. Int. Ed. 2004, 43, 2402-2406;
32. b) C. Nieto-Oberhuber, M. P. Muñoz, S. López, E. Jiménez-Núñez, C. Nevado, E. Herrero-Gómez, M. Raducan, A. M. Echavarren, Chem. Eur. J. 2006, 12, 1677-1693;
33. c) N. Cabello, E. Jiménez-Núñez, E. Buñuel, D. J. Cárdenas, A. M. Echavarren, Eur. J. Org. Chem. 2007, 4217-4223.
34. J. W. Faller, P. P. Fontaine, J. Organomet. Chem. 2006, 691, 1912-1918.
35. a) S. T. Diver, A. J. Giessert, Chem. Rev. 2004, 104, 1317-1382;
36. b) M. Mori, Adv. Synth. Catal. 2007, 349, 121-135.
37. C. Nieto-Oberhuber, S. López, E. Jiménez- Núñez, A. M. Echavarren, Chem. Eur. J. 2006, 12, 5916-5923.
38. C. Nieto-Oberhuber, S. López, M. P. Muñoz, D. J. Cárdenas, E. Buñuel, C. Nevado, A. M. Echavarren, Angew. Chem. 2005, 117, 6302-6304;
39. Angew. Chem. Int. Ed. 2005, 44, 6146-6148.
40. K. Ota, N. Chatani, Chem. Commun. 2008, 2906-2907.
41. S. López, E. Herrero-Gómez, P. Pérez-Galán, C. Nieto-Oberhuber, A. M. Echavarren, Angew. Chem. 2006, 118, 6175-6178;
42. Angew. Chem. Int. Ed. 2006, 45, 6029-6032.
43. C. H. M. Amijs, C. Ferrer, A. M. Echavarren, Chem. Commun. 2007, 698-700.
44. M. Schelwies, A. L. Dempwolff, F. Rominger, G. Helmchen, Angew. Chem. 2007, 119, 5694-5697;
45. Angew. Chem. Int. Ed. 2007, 46, 5598-5601.
46. A. Fürstner, L. Morency, Angew. Chem. 2008, 120, 5108-5111;
47. Angew. Chem. Int. Ed. 2008, 47, 5030-5033.
48. Interestingly, a gold carbene has been recently formed in the gas phase whose reactivity corresponds to that expected for a metal carbene: A. Fedorov, M.-E. Moret, P. Chen, J. Am. Chem. Soc. 2008, 130, 8880-8881.
49. C. A. Witham, P. Mauleon, N. D. Shapiro, B. D. Sherry, F. D. Toste, J. Am. Chem. Soc. 2007, 129, 5838-5839.
50. For the involvement of intermediates of type 5 in cyclizations couple with pinacol-type rearrangements, see: B. Baskar, H. J. Bae, S. E. An, J. Y. Cheong, Y. H. Rhee, A. Duschek, S. F. Kirsch, Org. Lett. 2008, 10, 2605-2607.
51. a) N. Chatani, K. Kataoka, S. Murai, N. Furukawa, Y. Seki, J. Am. Chem. Soc. 1998, 120, 9104-9105;
52. b) E. Mainetti, V. Mouriès, L. Fensterbank, M. Malacria, J. Marco-Contelles, Angew. Chem. 2002, 114, 2236-2239;
53. Angew. Chem. Int. Ed. 2002, 41, 2132-2135;
54. c) C. Nieto-Oberhuber, S. López, M. P. Muñoz, E. Jiménez-Núñez, E. Buñuel, D. J. Cárdenas, A. M. Echavarren, Chem. Eur. J. 2006, 12, 1694-1702;
55. d) S. López, E. Herrero-Gómez, P. Pérez- Galán, C. Nieto-Oberhuber, A. M. Echavarren, Angew. Chem. 2006, 118, 6175-6178;
56. Angew. Chem. Int. Ed. 2006, 45, 6029-6032.
57. C. Nieto-Oberhuber, S. López, A. M. Echavarren, J. Am. Chem. Soc. 2005, 127, 6178-6179;
58. C. Nieto-Oberhuber, P. Pérez-Galán, E. Herrero- Gómez, T. Lauterbach, C. Rodríguez, S. López, C. Bour, A. Rosellón, D. J. Cárdenas, A. M. Echavarren, J. Am. Chem. Soc. 2008, 130, 269-279.
59. Mixtures of stereoisomers were observed in the presence of water in the ring-expansion/Prins cyclization of 1,6-enynes bearing protected cyclopropanol groups at the alkyne moiety. The mixture could be a result of trapping of the intermediates by water, followed by a pinacol-type expansion: E. Jiménez-Núñez, C. K. Claverie, C. Nieto-Oberhuber, A. M. Echavarren, Angew. Chem. 2006, 118, 5578-5581;
60. Angew. Chem. Int. Ed. 2006, 45, 5452-5455.
61. a) See the Supporting Information for deuterium labeling experiments; b) See the Supporting Information for additional data.
62. [11b] whereas catalyst 11b gave a 1:3 mixture of these compounds.
63. [11b] see the corrigendum: C. Nieto-Oberhuber, M. P. Muñoz, S. López, E. Jiménez-Núñez, C. Nevado, E. Herrero-Gómez, M. Raducan, A. M. Echavarren, Chem. Eur. J. 2008, 14, 5096.
64. 2 solvent.
65. 4 (5 mol%) in MeOH under microwave irradiation (80°C, 30 min), 19b was obtained as a 1:1 mixture of diastereomers in quantitative yield. However, under these reaction conditions, the anti diastereomer epimerized to provide a 1:1 mixture of diastereomers.